ChE 125 Chemical Reaction Engineering Department of Chemical Engineering

Problem Set #1 University of the Philippines Diliman

PROBLEM 1
C. Cristallini, A. Villani, L. Lazzeri, G. Ciardelli, and A. S. Rubino [ Polym. Int., 48, 63-68 (1999)] used dilatometry to monitor
the kinetics of the homopolymerization of sodium acrylate in aqueous solution at 50°C . A cathetometer was employed to
generate the data tabulated below. The initial concentration of sodium acrylate is 0.4 M.

Time Height of meniscus Time Height of meniscus

(min) (cm) (min) (cm)
0 0.304 30 1.307
5 0.515 35 1.418
10 0.726 40 1.513
15 0.887 45 1.593
20 1.063 50 1.680
25 1.178 inf 3.617

Determine the order of sodium acrylate. What is the value of the rate constant?

PROBLEM 2
S. Mittal, V. Sharma, and K. Banerji [Int. J. Chem. Kinet., 18, 689-699 (1986)] studied the oxidation of propanol (A) with N-
chloroethylcarbamate (B) in acid solution:

A + 2B ® C + D + 2E
a. The following data are characteristic of this reaction at 30°C. Determine the integers that characterize the orders
of this reaction with respect to each of the reactants and the reaction rate constant.

A B x 103 Rate x 108

(mol/L) (mol/L) (mol/ L s)
0.5 2.0 2.66
0.5 5.0 6.15
0.5 7.5 9.45
0.5 10.5 12.60
0.5 12.5 15.40
0.5 15.0 17.85
0.1 5.0 1.25
0.2 5.0 2.46
0.3 5.0 3.78
0.7 5.0 8.65
0.9 5.0 11.30

b. Analyze the following values of the rate constant to determine the activation energy and frequency factor.

Temperature (°𝐶) Rate constant x 105

25 1.66
30 [from part (A)]
35 3.55
40 5.11
45 7.27
PROBLEM 3
S. D. Furrow [INt. J. Chem. Kinet., 14, 927-932 (1982)] studied the kinetics of the hydrozy iodination of 2-butenoic acid (B)
in aqueous solution:

2I 2 + B + I O3- + H + + 2H 2O ® 5C

1
a. Furrow used absorbance measurements to monitor the concentration of I 2 as a function of time for an experiment
in which the initial concentrations of I2, B, IO3-, and H+ were 1.98x10-4, 0.10, 0.025, and 0.10 M, respectively. If the
rate expression is of the form:

r = k(I 2 )m (B )n (I O3- )p (H + )q

Time I2 x 104 Time I2 x 104

(s) (mol/L) (s) (mol/L)
0 1.98 1060 0.856
35 1.94 1290 0.650
96 1.84 1530 0.479
232 1.68 1760 0.350
339 1.56 2000 0.250
588 1.28 2250 0.145
824 1.06 2500 0.063

where the various orders are either integers or half-integers, use the following data to determine the order of this
reaction with respect to I2, and the corresponding value of the pseudo-mth order rate constant. What assumptions
must be made to arrive at numerical values of these parameters?

b. From analyses of the type conducted to determine the order of the reaction with respect to I 2, Furrow reported
the values of the pseudo-mth order rate constant tabulated below.

IO3 B H+ kpseudo x 105

(M) (M) (M)
0.0250 0.025 0.0985 0.442
0.0250 0.005 0.0985 0.203
0.0250 0.100 0.0493 0.458
0.0250 0.100 0.0197 0.175
0.00625 0.100 0.0985 0.375
0.0500 0.100 0.0985 1.460